CN1204577C - Electrode material and method for producing the same - Google Patents

Abstract

Disclosed are electrode materials that exhibit very sharp pore size distribution within the range of mesopores and include pores having a pore diameter within a range of X+/- alpha nm (3.0 </= X < 10, alpha = 1.0; range of pore size distribution) of which volume accounts for 15% or more of the total volume of mesopores having a pore diameter within a range from 2.0 to 50 nm, and are suited for use in electric double layer capacitor, battery or the like of large capacitance and discharge of large current as well as a fabricating method thereof. These electrode materials are obtained by adding at least one transition metal or at least one transition metal compound to a carbon material or a carbon material precursor, and subjecting to a heat treatment at a temperature of 600 DEG C or higher.

Description

Electrode material and manufacture method thereof

Technical field

The present invention relates to electrode material and manufacture method thereof that battery and double-layer capacitor are used, and battery, double-layer capacitor, relate in particular to electrode material and the manufacture method thereof that double-layer capacitor is used that be suitable for most that has high static capacity and large current characteristic for formation.

Background technology

So far, as the material that various materials or ion etc. is absorption property, known have powdered activated carbon, granule activated carbon or a fibre active carbon, all has been widely used in various sorbing materials that various electrode material for battery or purifier, deodorization device and decolouring device etc. are filled and catalyst carrier etc.These activated carbon mainly are to make by activation processing in the presence of the steam or in the presence of zinc chloride and potassium hydroxide etc. for the material with carbon element of raw material from cocoanut shell, coal, timber, bamboo etc. so far, and have fine hole mostly.

About these minute apertures, generally the pore with the not enough 0.7nm of pore diameter is called the sub-micro hole; The pore of pore diameter 0.7-2.0nm is called micropore; The pore of pore diameter 2.0-50nm is called mesopore; Pore more than the pore diameter 50nm is called macropore.

Utilize activated carbon manufacture method so far, can make the activated carbon of the sub-micro hole prosperity that mainly is the micropore of pore diameter 0.7-2.0nm and the not enough 0.7nm of pore diameter; Pore diameter is that the formation of mesopore of 2.0-50nm is few, the pore volume ratio of mesopore not enough whole 10%.This activated carbon specific area is big and its molecular dimension is good less than the Molecular Adsorption ability of 2.0nm, but on the other hand, organic compound that uses as the electrolyte of double-layer capacitor or inorganic compound and these compound solvations and having can not be adsorbed or the desorption size becomes the shortcoming of big aggregation expeditiously.

And,, preferably make the activated carbon of the pore that only has specific dimensions from the absorption that adapts with the adsorbent molecular dimension or the viewpoint of desorption characteristic.But, with regard to mesopore,, but do not obtain having the sorbing material that special fine pore distributes in specific pore field.

In addition, though the activated carbon of the catalysis of adsorbed material on supporting various transition metal or transistion metal compound on the activated carbon and keeping by the catalytic decomposition activated carbon, and the electrode material with high static capacity all has report, but, as previously mentioned, with regard to mesopore, do not obtain having the activated carbon that supports transition metal of special pore distribution in specific pore zone.Also have, on activated carbon, support various transition metal or transistion metal compound, after making activated carbon, adsorb various transition metal or transistion metal compound, therefore, for example when immersing electrolyte used as electrode material, problems such as stripping carrying metal taking place, thereby can not get the electrode material that has abundant electrical characteristics and discharge and recharge stability.

In recent years, as stand-by power supply, accessory power supply be with the activated carbon electrode double-layer capacitor need sharp increase, and follow the development of electronic applications, rather the people attractes attention.

Also have, remove nearest memory ready power supply more the miniaturization, people wish to develop the high power capacity that uses as the vehicle mounted power supply, the storage battery of transient high-current supply accessory power supply.

The activated carbon specific area is big and chemically stability is high, so positive and negative two plates of the polarizing electrode of double-layer capacitor all use with the electrode material of activated carbon as main body.

Though the static capacity of double-layer capacitor is subjected to the influence of the specific area of electrode material, the packed density of electrode material and the internal resistance of electrode material etc., it is important particularly forming the size of the electrolyte ion in the electrolyte of electric double layer and the relation of electrode material pore size.

It is said in double-layer capacitor under the situation of the ammonium ion that uses so-called organic solvent system, phosphonium ion etc., above pore and the static capacity of the pore diameter 2nm of electrode material has relation, especially be in the electrolytical water system double-layer capacitor with sulfuric acid, can thinking that the above pore of pore diameter 2nm helps the performance of static capacity, current density etc.(3.0≤x＜10, α=1.0: the pore volume distribution of this pore diameter) has the activated carbon more than 15% of pore volume in pore diameter 2.0-50nm complete to pore diameter x ± α nm, is expected the good electrode material that the good electrode material used as double-layer capacitor or battery are used.

Also have, when in these activated carbon, having disperseed the activated carbon that is loaded with metal of transition metal or transistion metal compound to use to heavens as electrode material, the electrolyte that moves in electric double layer enters into the transition metal or the transistion metal compound of activated carbon, compare adsorbable bigger energy when therefore using separately with electric double layer.Therefore, (3.0≤x＜10, α=1.0: the pore volume distribution of this pore diameter) has complete middle more than 15% of pore volume of pore diameter 2.0-50nm to be expected pore diameter x ± α nm, contain the transition metal of 0.01-50wt% or the activated carbon of transistion metal compound, with electrode material or electrode material for battery etc., is good as double-layer capacitor.

The formed electric double layer thickness of the ion that adsorbs on the pore surface by electrode material is about about 1nm, therefore be more than the 2nm as the aperture that on thin also surface, can form the pore of electric double layer equally, so be not suitable for the electrode material used as high static capacity and heavy-current discharge based on the existing activated carbon of the micropore below the 2nm.Especially, also can think: in existing activated carbon with the following micropore of a lot of 2nm, the speed that moves in pore such as the electrolyte ion of solvation is slow, and this also can think not to be suitable for the main cause of the electrode material that high static capacity and heavy-current discharge use.

Thereby, in existing activated carbon, support in the activated carbon of transition metal or transistion metal compound based on the micropore below the 2nm, owing on the pore inner surface, do not form reasons such as the translational speeds in minute aperture such as electric double layer and electrolyte ion are slow equally, just can not in transition metal or transistion metal compound, adsorb big energy and utilize this energy expeditiously.This can think: the activated carbon that supports transition metal or transistion metal compound in the existing activated carbon is not suitable for doing the main cause of the electrode material of high static capacity and heavy-current discharge.

Also have, metal-halogen cell, for example zinc-Zn-Br battery is owing to have many advantages, such as the two poles of the earth active material aboundresources and low price, the theoretical energy density height is for the liquid circular form is adjusted battery output and easily owing to be low-temperature working water solution system battery, so maintenance management etc. easily, thereby obtain exploitation rapidly in recent years, study as effective material with activated carbon as finish materials.Yet, for realizing this battery practicability, the some problems of also essential solution.Halogen reduction reaction in the positive pole when wherein also comprising discharge how, and how carry out rapidly and effectively? these all directly influence the energy efficiency of battery, therefore, as the electrode material of positive pole usefulness with the pore of the activated carbon that uses, just become the important techniques problem as main body with the mesopore more than the diameter 2nm.

Up to now, so that becoming the big sorbing material of making the bigger material of adsorbable molecular diameter, the pore of activated carbon carried out various tests.For example, have by several times repeatedly activation procedure make pore diameter become big method.But in this manufacture method, because the pore volume ratio in the mesopore zone of occupying in full pore volume is low, and through activation procedure repeatedly, productive rate still descends, so undesirable.

In addition, open the method that discloses a kind of carbon fiber modifying in the flat 5-302216 communique, that is, utilize oxidant to contrast surperficial 0.1-1200m the spy ²After the carbon fiber dehydration processing of/g, make it support alkaline-earth metal, carry out activation processing.In this method of modifying, in the 1.5-15nm scope of aperture, form pore, (3.0≤x＜10, α=1.0: but the pore volume distribution of this pore diameter) accounts for less than 15% of the complete middle pore volume of pore diameter 2.0-50nm pore diameter x ± α nm, thereby can not carry out the strict control of material with carbon element fine structure.This material with carbon element has following shortcoming, that is, distribute owing to have widely pore, removes the pore of effectively absorption to also have unnecessary pore, therefore exist adsorption efficiency at the bottom of, fibre density minimizing and the also low shortcoming of intensity.

Also have, disclosed active carbon material in the Te Kaiping 5-000811 communique is owing to be with protein or proteinaceous mud or waste product, be raw material perhaps with polyacrylonitrile fibre shape activated carbon, so contain a lot of impurity, and only carry out activation processing with carbonization or steam, carbon dioxide and oxygen etc., therefore have and can't carry out tight shortcomings such as fine pore control.Especially, conductivity is low because carbon purity is low, so also uncomfortable as electrode material.

Also have, the spy opens to disclose in the flat 5-2946007 communique and will be made the manufacture method of the activated carbon that contains metal by the mixture that low softening point asphalt and metal oxide are formed through carbonization treatment and activation processing.Its present situation is: this method does not have to make pore diameter x ± α nm yet, and (3.0≤x＜10, α=1.0: the pore volume distribution of this pore diameter) accounts for complete middle more than 15% of pore volume of pore diameter 2.0-50nm.And, also owing to the rare-earth compounds that has used ytterbium compound and/or yttrium compound etc., so the cost of material height is uneconomical.

Also have, Te Kaiping 4-294515 communique discloses absorption energy element and spy and has opened flat 6-503924 communique and disclose ultra-capacitor, these two parts of applications all are that the carbon porous body of activated carbon etc. is combined with transition metal or transistion metal compound, but kind electrode material, (3.0≤x＜10, α=1.0: the pore volume distribution of this pore diameter) does not reach more than 15% of pore volume in pore diameter 2.0-50nm complete to its pore diameter x ± α nm, is unsuitable for doing the electrode material that high static capacity, heavy-current discharge are used.In addition, also owing to utilizing the described manufacture method of above-mentioned communique that a large amount of transition metal or transistion metal compound are combined with the carbonaceous porous body of activated carbon etc., therefore when the transition metal that makes this carbonaceous porous body and high concentration or transistion metal compound solution contact, the dispersion of transition metal or transistion metal compound is insufficient, therefore generate transition metal or transistion metal compound aggregation block, the micropore of this carbon porous body takes place inaccessible, transition metal or transistion metal compound that physical absorption only takes place on the pore surface of this carbonaceous porous body simultaneously are dissolved in the electrolyte, therefore in that the performance during with electrode material can not obtain satisfied fully used as double-layer capacitor.

As mentioned above, present situation is, form in the existing method of pore in the mesopore zone, the pore volume that does not obtain the scope of pore diameter x ± 1.0nm (3.0≤x＜10) has the electrode material more than 15% of the complete middle pore volume of pore diameter 2.0-50nm, so can not carry out tight pore control fully.Therefore, the electrode material 15% or more of the pore volume that supports pore diameter x ± 1.0nm (3.0≤x＜10) scope of transition metal or transistion metal compound with pore volume in pore diameter 2.0-50nm complete also can not obtain.

Summary of the invention

The present invention finishes for solving above-mentioned variety of issue, its purpose is: a kind of electrode material is provided, have active carbon and on active carbon, support transition metal or transistion metal compound, it is characterized in that, pore diameter x ± α nm, wherein, 3.0≤x＜10, α=1.0, pore volume account for more than 15% of pore volume in pore diameter 2.0-50nm complete, and contain transition metal or the transistion metal compound of 1-50wt% in the electrode material.And electrode material preferably has the diffraction maximum from graphite crystal that is obtained by X-ray diffraction.In addition, another object of the present invention is to the battery or the double-layer capacitor that manufacturing method of electrode material of the present invention are provided and utilize this electrode material.

The inventor etc. have carried out research with keen determination for addressing the above problem, it found that: by add a kind of transition metal or transistion metal compound at least in material with carbon element and/or material with carbon element predecessor after, in nonoxidizing atmosphere, carrying out carbonization under the temperature more than 600 ℃ or under weak oxide thing atmosphere, activating, (3.0≤x＜10, α=1.0: the pore volume distribution of this pore diameter) accounts for the electrode material more than 15% of the complete middle pore volume of pore diameter 2.0-50nm, thereby has finished the present invention to have obtained pore diameter x ± α nm.And then, found again: a kind of like this electrode material is provided, it is characterized in that, in this scope, has the maximum that fine pore distributes, have by X-ray diffraction to the diffraction maximum that derives from graphite crystal and contain 0.01-50wt%, be preferably transition metal or the transistion metal compound of 1-50wt%, thereby finish the present invention.

Promptly, (3.0≤x＜10, α=1.0: the pore volume distribution of this pore diameter) accounts for the electrode material more than 15% of the complete middle pore volume of pore diameter 2.0-50nm to the invention provides a kind of pore diameter x ± α nm, and then, the invention provides the maximum that in this scope, has pore-size distribution, and the electrode material by the resultant diffraction maximum from graphite crystal of X-ray diffraction is arranged.The transition metal that contains 0.01-50wt% or the electrode material of transistion metal compound also are provided.Also have, the present invention also provides these manufacturing method of electrode material, or utilizes this electrode material can high static capacity and the double-layer capacitor or the high capacity cell of heavy-current discharge.

Though it is unclear that the mesopore of electrode material of the present invention forms mechanism, but can be speculated as: during heat treatment because the catalytic action of transition metal, carbon skeleton around the transition metal is in a single day destroyed, the reaction speed of activated gas and carbon rises significantly, and becoming the state that transition metal is subjected to etch just, minute aperture forms, enlarges and carries out zoarium and form mesopore.Also can infer: the mesopore size of this formation is relevant with the transition metal atoms size.Also can think: the atomic rearrangement when forming owing to mesopore forms the part graphite crystal.In addition, above-mentioned transition metal is selected from copper, iron, cobalt or nickel.

Description of drawings

The curve chart that Fig. 1 distributes for expression sample 1,2,3,5 fine pore of the present invention.

Fig. 2 is the curve chart of the fine pore distribution of expression sample 26 of the present invention.

Fig. 3 is the curve chart of the fine pore distribution of expression sample 27 of the present invention.

Fig. 4 is the curve chart of the fine pore distribution of expression sample 28 of the present invention.

Fig. 5 is the curve chart of the fine pore distribution of expression sample 30 of the present invention.

Fig. 6 is the curve chart of the X-ray diffraction image of expression sample 26,27,28,30 of the present invention.

Fig. 7 is the key diagram of double-layer capacitor of the present invention.

Fig. 8 is the key diagram that is used for the water system double-layer capacitor of electrode material evaluation of the present invention.

Fig. 9 is the key diagram that is used for the organic system double-layer capacitor of electrode material evaluation of the present invention.

In above-mentioned accompanying drawing, all be added with symbol, wherein 1-electrode material, 2-collector body, 3-division board, 4-liner, 5-terminal board, 6-shell, 7-capacitor.

Embodiment

Electrode material of the present invention distributes by have fine pore in specific scope, can be used for double-layer capacitor or battery etc., and promptly absorption or desorption electrolyte ion etc., and can demonstrate very high adsorption capacity to them.In addition, (3.0≤x＜10, α=1.0: the pore volume distribution of this pore diameter) is with 0.01-0.50cm for pore diameter x ± α nm ³/ g is desirable; With 0.050-0.50cm ³/ g is better; With 0.10-0.50cm ³/ g is for the most desirable.If in the pore volume of this scope less than 0.010cm ³During/g, the adsorption capacity of electrolyte ion diminishes, and owing to static capacity has also diminished, so undesirable.In addition, the pore volume of this scope accounts for complete middle more than 15% of pore volume of pore diameter 2.0-50nm, accounts for 20-95% for desirable, and it is better to account for 30-95%.In less than pore volume in pore diameter 2.0-50nm complete 15% o'clock of the pore capacity of this scope, static capacity and the attached speed of electrolytic ion adsorption and desorption diminish, and are unfavorable.

Also have, electrode material of the present invention is except that above-mentioned feature, and best is, has the diffraction maximum from graphite crystal (002) face in the X-ray diffractogram of Cu-K α line near 2 θ=26 °.In addition, being characterized as of electrode material of the present invention: even when being initial feed, preferably make a part of material with carbon element graphitization with difficult graphite voltinism carbon or its predecessor.As previously mentioned, the appearance from the diffraction maximum of graphite crystal means at least a portion graphitization, can be speculated as owing to improve crystallinity, and fine pore distributes and becomes more clear.

Also can think: conductivity has also been improved, and helps the reduction of double-layer capacitor internal resistance.Also have, the heat treatment that difficult graphited carbon carries out more than 2000 ℃ usually also is difficult to graphitization, still, can carry out graphitization with comparalive ease according to the present invention, and improve characteristics such as fine pore distributing homogeneity, conductivity and thermal conductivity.

Also have, electrode material carbon content rate of the present invention is to be desirable more than the 90wt%, and 93wt% is better, and 95wt% is the most desirable.Carbon content rate 90wt% forms with the pore that upper electrode material carries out carbonization, the direct capacitance quantitative change is big, and have the characteristic of the carbon electrode material of what is called good conductivity, corrosion resistance and thermal conductivity etc., therefore when using as the double-layer capacitor electrode material, internal resistance is low to be desirable.In addition, from static capacity and conductivity viewpoint, the not enough 1wt% of nitrogenous rate was desirable.

Also have, electrode material of the present invention, transition metal or transistion metal compound total content are 0.01-50wt%, and 0.1-20wt% is desirable, and 1-10wt% is even more ideal.The content of transition metal or transistion metal compound can not obtain the electrolyte of quantity sufficient, the electrode material that can not obtain having high static capacity during less than 0.01wt%.If the content of transition metal or transistion metal compound during greater than 50wt%, produces micropore, the mesopore obturation of activated carbon, therefore, can not get having the electrode material of high static capacity.

Electrode material of the present invention is because the field of employment is different with user mode, can be Powdered, different shapes such as graininess, cylindric, spherical, broken shape, porous type bulk or sheet use.Be shaped as under pulverous situation, average grain diameter is generally 0.10-200 μ m, and 1.0-100 μ m is desirable, and 5-50 μ m is even more ideal; The particle volume density is 0.7-2.3g/cm ³, 0.8-1.8g/cm ³Be desirable, but be not particularly limited.

In addition, be shaped as under the situation of broken shape, as material with carbon element carbide such as ion exchange resin, cocoanut shell, coal made the indefinite shape of pulverizing, its average grain diameter is generally 1-100 μ m, and 5-50 μ m is desirable; The particle volume density is 0.7-2.3g/cm ³, 0.8-1.8g/cm ³Be desirable, but be not particularly limited.

Electrode material specific area of the present invention is 100-2500m ²/ g is desirable, 200-2300m ²/ g is even more ideal, 300-2000m ²/ g is ideal, but is not particularly limited.

Also have, the invention provides above-mentioned manufacturing method of electrode material.Promptly, after in material with carbon element or material with carbon element predecessor, adding a kind of transition metal or transistion metal compound at least, by activating under carbonization or the weak oxide atmosphere carrying out under the nonoxidizing atmosphere under the temperature more than 600 ℃, can make electrode material of the present invention.Be used for material with carbon element that electrode material of the present invention makes preferably cocoanut shell, coke, charcoal, resin carbonation thing, bamboo carbide.And, in the resin carbonation thing, preferably make spent ion exchange resin carbide or phenolic resins carbide.Though the specific area value indefinite of these material with carbon elements is with less than 30m ²/ g is for well.

In addition, be used for electrode material of the present invention and make employed material with carbon element forerunner animal preferably cocoanut shell, coal, timber, bamboo and resin.As timber, for example preferably use with various broad leaf trees and coniferous tree trees and waste material and sawdust etc. as raw material.There is not particular determination though become the resin of the predecessor of resin carbonation thing, except that various ion exchange resin, the thermosetting resin of phenolic resins, melmac, urea resin, furane resins etc. preferably.

Phenolic resins if roughly distinguished, can be divided into resol resin and Novolac resin and special phenolic resins or modified product etc.Melmac be in the presence of base catalyst by melamine and aldehyde, be generally formaldehyde and react resulting water white water-soluble resin.Urea resin is by urea and the resulting water white water-soluble resin of formolite reaction in the presence of acid catalyst or base catalyst.Furane resins are initial stage condensation product, Furan Aldehydes resin or their modified resin etc. of furfural alcohol.

As thermosetting resin used in the present invention, to handle easily when making, with regard to the control etc., phenolic resins is desirable easily for carbonization productive rate height and pore, especially following granular phenol resin is the most desirable.

That is to say that this granular phenol resin is open in public clear 62-30210 communique of spy or special public clear 62-30212 communique etc., is that the condensation product with phenols and aldehyde is the granular resin of main component.This phenolic resins has following feature: (A) contain spherical primary particles of 0.1-150 μ m and secondary aggregation thereof; (B) all at least 50wt% can be by the size of mesh 150 μ m sieve; (C) in specification, define, solubility metal is below the 50wt%; (D) as the measured value of liquid chromatogram, the free phenol aldehyde is below the 100ppm.Granular phenol resin with above-mentioned feature is desirable especially.

Though the ion exchange resin as employed material with carbon element predecessor among the present invention is not particularly limited, but can use with gel or porous type or the high porous type storng-acid cation exchange resin of styrene diethylene benzene copoly mer as matrix, be to give the porous type of functional groups such as imido-acetic acid base, poly-amino, amino, phosphate, dithiocarbamate-based and oximido or the chelating resin of high porous type in the macromolecule matrix to polystyrene, acrylic acid series, phenol perhaps.

Cation exchange resin is the polymer acid that is combined with the acidic groups of acid hydroxy group, carboxyl, sulfonic group etc. on substrate synthetic resin, carry out ion-exchange with the transition metal ions in the solution, and make a large amount of transition metal ions high degree of dispersion and can support, therefore can rightly it be used as carbon predecessor used in the present invention.

In the present invention, in above-mentioned material with carbon element of 100 weight portions or material with carbon element predecessor, add a kind of transition metal at least or metallic compound 0.01-100 weight portion is desirable, 0.5-80 weight portion is better, the 2-60 weight portion is the most desirable, and under temperature more than 600 ℃, carry out carbonization or activation, can make electrode material.

Here a kind of transition metal that is added or transistion metal compound are any or two or more material in the nitrate, acetate, sulfate, carbonate, bromide, chloride, oxide, hydroxide of metal dust or metal, are desirable.If this metal pulverulence then it would be desirable the sieve that its all 95wt% can be by mesh 150 μ m, and even more ideal be that average grain diameter is the powder of 0.3 μ m size.In addition, in the nitrate of metal, acetate, sulfate, carbonate, bromide, chloride, oxide, hydroxide under the situation of arbitrary material, easy to handle concentration solution also can use as solution with the polarity flux of its aqueous solution or methyl alcohol etc. during as suitable the manufacturing.Also having, as transition metal, for example use with symbol of element Cu, Fe, Co, Ni, Ti, Cr, the represented metal of Mn, W, is desirable.

In the present invention, as in material with carbon element or material with carbon element predecessor, adding the above-mentioned transition metal or the method for this transistion metal compound, for example under the situation of metal dust, can directly mix stirring with the material with carbon element or the material with carbon element predecessor of its specified rate.Also have, when above-mentioned transistion metal compound, the metallic compound of specified rate made solution in the aqueous solution or methyl alcohol polar solvent after, can add in material with carbon element or the material with carbon element predecessor and mix.During interpolation, solution is made low concentration, material with carbon element or material with carbon element predecessor are added to the 200-500 weight portion, under slurry form, mix dry also the removing in back and desolvate, also can carry out carbonization or activation then; During interpolation, material with carbon element or material with carbon element precursor are for example made the 5-100 parts by weight solution, under the clay state, carry out after the mixing mixing dryly and remove and desolvate, also can carry out carbonization or activation.

When in the material with carbon element predecessor, adding various metal dust, directly use its specified rate to mix.In addition, when adding various metallic compound, described carbon predecessor is used addition, the specified rate that is converted into by transition metal mixes.When the material with carbon element precursor is dissolved in the high solvent such as the polarity of water, methyl alcohol etc., after making solution, adds in the material with carbon element precursor solution and mix by the aqueous solution or methyl alcohol isopolarity solvent.Resulting mixture carries out carbonization or activation after super-dry.

In the present invention, owing to carry out carbonization or activation after adding transition metal or transistion metal compound to material with carbon element or material with carbon element predecessor, therefore can think: different with the situation of on activated carbon, adsorbing transition metal or this metallic compound and support, all or part of of transition metal or this metallic compound becomes the state within the carbon structure of imbedding activated carbon securely, therefore activated carbon is used as electrode, even under the situation that immerses electrolyte, the stripping that also is difficult to produce transition metal or this transistion metal compound.When this stripping is a problem, by pickling as described later, remove after the transition metal or this transistion metal compound of stripping in advance, it is used as electrode material, be desirable.

As the method for adding various transistion metal compounds in the employed ion exchange resin among the present invention, can be undertaken by following ion-exchange, for example, in the ion exchange resin that exchange is added in the tubing string, feed the solution that contains various transition metal ionss, utilize this exchange column method to carry out ion-exchange, perhaps utilize the dipping method in the aqueous solution that ion exchange resin is immersed in contain various transition metal ionss to carry out ion-exchange.When utilizing above-mentioned these methods, owing in this resin, a large amount of transition metal is supported, so be a kind of suitable especially method as the manufacture method of material with carbon element presoma of the present invention with high dispersion state.

At least material with carbon element or this material with carbon element compound of above-mentioned a kind of transition metal or transistion metal compound have been added, by under nonoxidizing atmosphere in more than 600 ℃, it is desirable to 700-2000 ℃, even more ideal be to carry out carbonization below 800-1500 ℃, perhaps after carbonization by under the weak oxide atmosphere in more than 600 ℃, it is desirable to 700-1500 ℃, even more ideal be under 800-1200 ℃, to activate, can make electrode material of the present invention.When carburizing temperature is lower than 600 ℃, the pore that can not carry out transition metal forms, and (3.0≤x＜10, α=1.0: the pore volume distribution of this pore diameter) has the electrode material more than 15% of the complete middle pore volume of pore diameter 2.0-50nm to can not get pore diameter x ± α nm.In addition, also can not carry out pore because carbonization is insufficient and form, so conductivity is low and thermal endurance and drug-resistant performance are all low, be unfavorable.When using as the electrode material of double-layer capacitor since electrolyte ion absorption easily and absorption or desorption speed little, so static capacity is little, especially be unsuitable for heavy-current discharge.

In addition, so-called here nonoxidizing atmosphere is meant to contain the atmosphere that nitrogen, helium, argon, hydrogen or carbon monoxide are gas, is actually the atmosphere of oxygen-free voltinism gas.Also have, so-called weak oxide atmosphere is meant and contains with steam and CO ₂Be the atmosphere of main gas, comprise that also part contains the situation of nitrogen, helium, argon, hydrogen or CO, these belong within the scope of the invention.

Do not have special restriction though reach the programming rate of the maximum processing temperature in carbonization and the activation procedure, it is desirable to 5-500 ℃/H, that ideal is 10-300 ℃/H.The retention time of the atmosphere during carbonization, programming rate, maximum temperature and maximum temperature etc. should be considered the kind of kind, pore structure, material with carbon element precursor of material with carbon element or characteristic and wait as the pore structure of the electrode material of purpose to select optimum condition.Usually in order to form pore, it is desirable being warmed up to higher temperature, and still, if maximum temperature is too high, then pore volume reduces and electrode characteristic reduction and undesirable because pore is meticulous.

Electrode material through carbonization and activation process manufacturing, it is desirable adjusting contained transition metal amount as required, but, in this case, after pickling such as watery hydrochloric acid, rare nitric acid, with ammonia spirit etc. neutralize, cleaning composite type ground such as washing, ion-exchange, distilled water and ultra-pure water carries out, and the transition metal that is contained is decided to be specified rate.Because the effect of contained transition metal has promoted employed electrolyte decomposition, so just generation causes pressing in the capacitor increase, cycle characteristics reduction owing to decomposition gas takes place, so in order to prevent above-mentioned situation, preferably clean fully.

According to the present invention resulting electrode material be generally Powdered, graininess, broken shape, cylindric, spherical, porous type is block or sheet, (3.0≤x＜10, α=1.0: the pore volume distribution of this pore diameter) accounts for complete middle more than 15% of pore volume of pore diameter 2.0-50nm to pore diameter x ± α nm, and the maximum that in this scope, has pore to distribute, have by the resulting diffraction maximum of X ray, and contain transition metal or the transistion metal compound of 0.01-50wt% from graphite crystal.

Also have, the invention provides the battery and the double-layer capacitor that use described electrode material.This capacitor basically as shown in Figure 7, with electrode material 1 and collector body 2 as the unit pole polarizing electrode, and by these two polarizing electrodes and between two electrodes set division board 3 by the electrolyte dipping constitute, can constitute by these component units are in parallel or series connection lamination if desired.

Use the porous plate of anti-electrolyte as division board, for example can use porous plate or nonwoven fabrics such as polyethylene, teflon (polytetrafluoroethylene) and polypropylene.

The electrolyte of double-layer capacitor requires to have high electrochemical stability in wide temperature range.For example can use propyl carbonate, ethylene carbonate, butyl carbonate, gamma-butyrolacton, N as solvent, dinethylformamide, sulfolane, 3-methyl sulfolane, water etc.; Can use LiBF as solute ₄, Me ₄NBF ₄, Et ₄NBF ₄, LiPF ₆, Me ₄NPF ₆, Et ₄NPF ₆, LiClO ₄, Me ₄NClO ₄, EtNClO ₄, H ₂SO ₄Deng.If when electrolyte is non-water system, then notes and contain moisture.The dipping of electrolyte fully soaks electrode material and division board by vacuum or heating dipping.

Electrode material of the present invention, its pore diameter x ± α nm (3.0≤x＜10, α=1.0: the pore volume distribution of this pore diameter) accounts for complete middle more than 15% of pore volume of pore diameter 2.0-50nm, in this scope, has the maximum that fine pore distributes, and have by the resultant diffraction maximum of X-ray diffraction from graphite crystal, and the transition metal or the transistion metal compound that contain 0.01-50wt%, therefore, the organic system electrolyte ion, inorganic is electrolyte ion, especially the absorption that becomes big electrolyte ion aggregation etc. of solvation and molecular dimension conciliate adsorption rate and adsorption capacity big, especially conductivity is good, therefore as double-layer capacitor, when electrode materials such as metal-halogen cell use, these static capacities and discharging current all can improve etc., so with it as double-layer capacitor, electrode materials such as metal-halogen cell are exceedingly useful.

Determination method

In the pore determination method of porous material such as carbon, pottery, all gases absorption method, mercury platen press are arranged usually, can select the optimum determining method according to the size of pore.After determination method and analytic method are specified in.Electrode material of the present invention, (3.0≤x＜10, α=1.0: the pore volume distribution of this pore diameter) accounts for complete middle more than 15% of pore volume of pore diameter 2.0-50nm to its pore diameter x ± α nm, and usually adopts parsing routine for the pore volume that comprises this scope 0.7-50nm left and right sides scope, be to use the liquid nitrogen absorption method of liquid nitrogen temperature to resolve.

The mensuration of the fine pore distribution of electrode material of the present invention, pore volume, specific area is to use the nitrogen adsorption method of full-automatic gas phase determining adsorption device BELSOP28 (Japanese Bel (BEL) Co., Ltd. system) by liquid nitrogen temperature to carry out.The pore volume of pore diameter 2.0-50nm is obtained by the method for Dollimore-Heal.This method supposition pore is shaped as cylindric, and the method for utilizing desorb fine pore distribution isotherm to calculate.

Below carry out the generality explanation.

1. fine pore distributes and the mensuration of pore volume

Cylindric pore radius is represented by following (1) formula:

rp＝t+rk (1)

In the formula, rp: pore radius

Rk: the core radius of concave-convex lens part

T: the adsorbent layer thickness of pressure p.

The thickness of adsorption layer is obtained by the t-plot of standard specimen, and core radius is obtained by Kelvin formula (2):

ln(p/po)＝-(2rVL/rmRT)cosθ (2)

In the formula, p: equilibrium pressure

Po: saturated vapour pressure

R: surface tension of liquid

VL: liquid molar volume

Rm: concave-convex lens radius

R: gas constant

T: measure temperature

θ: the contact angle of liquid and pore

Concave-convex lens when supposing desorption equates with core radius, during the nitrogen of liquid nitrogen temperature, for:

rk(nm)＝0.4078/log(po/p) (3)

The fine pore of pore diameter 2.0-50nm distributes, pore volume is obtained as stated above.

2. the mensuration of specific area

The measurement result of the nitrogen adsorption isotherm of liquid nitrogen temperature is put in order according to (4) formula, obtained the monolayer adsorbance, and by nitrogen molecular occupied area (0.162nm ²) the BET multipoint method of obtaining specific area carried out specific area measuring.

p/V(pO-p)＝(1/vmC)+{(C-1)/vmC}(p/pO) (4)

S＝vmσN (5)

In the formula, P: equilibrium pressure

PO: saturated vapour pressure

V: the adsorbance of equilibrium pressure

Vm: monolayer adsorbance

C: constant

S: specific area

σ N: nitrogen unimolecule occupied area

3.Cu-K the X-ray diffraction of α line is measured

The electrode material X-ray diffraction of trial-production is measured and is used X-ray diffraction device RINT-1400 (Rigaku Denki Co., Ltd's system), and the pipe ball uses Cu-K α line, graphite monochromator, is undertaken by the reflective powder method.

4.CHN elementary analysis

Use CHN encoder MT-5 (Co., Ltd.'s system of this making of willow) to be undertaken by micro-organic elemental analysis.In addition, measure by 1CP and to calculate the transition metal or the transistion metal compound that are supported and contain concentration, and the full amount of element of its deduction is decided to be 100% is represented.

5. transition metal or transistion metal compound contain concentration determination

Put into platinum crucible after 2 hours the accurate weighing of sample 1gr of drying down with 105 ℃, and, on hot plate, heat to adding about 1-2ml hydrofluoric acid through 2 hours in the ashing sample at 700 ℃.Before doing admittedly, add nitric acid doubly with ultra-pure water dilution 7-8.Add ultra-pure water about liquid measure reaches 1/3 again, after adding the about 1ml of nitric acid and heating 1 hour, it is quantitative to add ultra-pure water 50ml.Make blank assay, the measurement result of proofreading and correct each sample by same operation.Quantitatively be to use described solution, the 1CP emission spectrographic analysis of using Hitachi's (strain) to make double-deck monochromatic ICP emission spectrum device P-5200 type is carried out.

6. the mensuration of static capacity

(1) uses the electrolytical evaluation of water system

Measured static capacity by the water system double-layer capacitor of embodiment made.Between the two poles of the earth of double-layer capacitor, apply 0.9V, and carry out constant voltage charging in 6 hours, carry out constant current discharge, make voltage drop to 0.45V, obtain the capacity of Electric double-layer capacitor measuring device according to the required time of this decline by 0.54V with 100 μ A.According to the static capacity of this double-layer capacitor and the weight of one group of polarizing electrode, obtained the static capacity of electrode material Unit Weight.By implementing this mensuration repeatedly, carried out the evaluation of charging and discharging cyclical stability.

(2) use the electrolytical evaluation of organic system

Measured static capacity by the double-layer capacitor of embodiment made.Apply 4.0V between the two poles of the earth of double-layer capacitor, constant current discharge is carried out with 5mA in the discharge back, has obtained the static capacity of double-layer capacitor.According to the static capacity of this double-layer capacitor and the weight of one group of polarizing electrode, obtained the static capacity of electrode material Unit Weight.Carried out charging and discharging cyclical stability mensuration by implementing this mensuration repeatedly.

7. the mensuration of volume change rate

Except that the discharge with constant current is decided to be 1000 μ A, estimate the identical static capacity of obtaining with having used the electrolytical static capacity of above-mentioned water system, this value is decided to be C ₁₀₀₀, the static capacity that 100 μ A discharge is obtained is decided to be C ₁₀₀, calculated volume change rate (Δ C) by following formula:

ΔC＝(C ₁₀₀₀-C ₁₀₀)/C ₁₀₀×100

Followingly specifically describe the present invention, but the present invention is not only limited to these embodiment according to embodiment.

Embodiment

The manufacturing of electrode material of the present invention

Embodiment 1

For the granular phenol resin of the average grain diameter 20 μ m of 100 weight portions (Kanebo Ltd: Bellpearl R800) add to convert and become the cobalt chloride solution of the such adjustment over-richness of given addition with Co, fully mix by mixer, following dry 24 hours in 110 ℃ in atmosphere.Dry sample is placed in the electric furnace, programming rate with 50 ℃/hour under blanket of nitrogen is warming up to 1000 ℃, and maintenance was cooled off after 5 hours under this temperature, and having manufactured experimently addition is the carbonization sample of 0.2 weight portion (carbonization sample 1), 1 weight portion (carbonization sample 2), 5 weight portions (carbonization sample 3), 10 weight portions (carbonization sample 4), 120 weight portions (carbonization sample 5).

Also have, in raw material, use specific area 1500m ²Carbon particulate of/g, carry out same operation, having obtained the Co addition is the carbonization and activation sample of 0.2 weight portion (carbonization sample 6), 1 weight portion (carbonization sample 7), 5 weight portions (carbonization sample 8), 120 weight portions (carbonization sample 9) and 0.2 weight portion (activation sample 10), 1 weight portion (activation sample 11), 5 weight portions (activation sample 12), 120 weight portions (activation sample 13).Also have, activation is to have carried out 1 hour in 800 ℃ under hydrogen/steam (=1/1) mixed-gas atmosphere, and sample 1-24 in turn fully cleans and removes after the remaining Co with rare nitric acid, ion exchange water, distilled water, carries out 3 hours dryings under 115 ℃.

Measured X-ray diffraction by pore distribution, pore volume and the Cu-K α line of the sample of making as mentioned above.It the results are shown in table 1.In this table, (3.0≤x＜10, α=1.0: the pore volume distribution of this pore diameter) is with V with pore diameter x ± α nm ₁Expression; With the full mesopore pore volume of pore diameter 2.0-50nm with V ₀Expression.In addition, will be for pore diameter x ± α nm (3.0≤x＜10, α=1.0: this pore volume (V ₀) the following V of ratio ₁/ V ₀(%) expression.

As seen from Table 1, taking the granular phenol resin as the carbonization sample 2,3,4 of raw material carbonization trial-production, be the carbonization sample 7,8 of raw material carbonization trial-production and activate in the activation sample 11,12 of trial-production with carbon particulate, (3.0≤x＜10, α=1.0: the pore volume distribution of this pore diameter) accounts for complete middle more than 15% of pore volume of pore diameter 2.0-50nm to pore diameter x ± α nm, and has the maximum of pore distribution clearly within this scope.

Table 1

Sample		Raw material (weight portion)		Co addition (weight portion)	Heat-treat condition (temperature * time)	The pore diameter (nm) of the maximum that fine pore distributes
							The carbonization sample	1	Phenolic resins	100	0.2	1000 ℃ * 5H carbonization	0.7
The carbonization sample	2	Phenolic resins	100	1	1000 ℃ * 5H carbonization	3.9
							The carbonization sample	3	Phenolic resins	100	5	1000 ℃ * 5H carbonization	4.0
The carbonization sample	4	Phenolic resins	100	10	1000 ℃ * 5H carbonization	4.2
							The carbonization sample	5	Phenolic resins	100	120	1000 ℃ * 5H carbonization	34.8
The carbonization sample	6	Carbon particulate	100	0.2	1000 ℃ * 5H carbonization	0.8
							The carbonization sample	7	Carbon particulate	100	1	1000 ℃ * 5H carbonization	4.0
The carbonization sample	8	Carbon particulate	100	5	1000 ℃ * 5H carbonization	4.0
							The carbonization sample	9	Carbon particulate	100	120	1000 ℃ * 5H carbonization	40.0
The activation sample	10	Carbon particulate	100	0.2	800 ℃ * 1H activation	1.7
							The activation sample	11	Carbon particulate	100	1	800 ℃ * 1H activation	4.0
The activation sample	12	Carbon particulate	100	5	800 ℃ * 1H activation	4.0
							The activation sample	13		100	120	800 ℃ * 1H activation	23.4

Sample		The pore volume of pore diameter X ± 1.0nm (V1)	The complete middle pore volume (V0) of pore diameter 2.0-50nm	V1/V0 (％)	Specific area (m 2/g)	X ray is identified thing
							The carbonization sample	1	0.006	0.111	5.4	22	Co
The carbonization sample	2	0.048	0.117	41.0	625	Co、C
							The carbonization sample	3	0.099	0.175	56.6	587	Co、C
The carbonization sample	4	0.037	0.106	34.9	364	Co、C
							The carbonization sample	5	0.005	0.075	6.7	155	Co
The carbonization sample	6	0.013	0.095	13.7	1486	Co
							The carbonization sample	7	0.046	0.103	44.7	1510	Co、C
The carbonization sample	8	0.098	0.334	29.3	1415	Co、C
							The carbonization sample	9	0.006	0.109	5.5	746	Co
The activation sample	10	0.014	0.105	13.3	1759	Co
							The activation sample	11	0.035	0.102	34.3	1709	Co、C
The activation sample	12	0.141	0.368	38.3	1567	Co、C
							The activation sample	13	0.079	0.635	12.4	1055	Co

X: pore diameter 3≤X＜10 5H: heating time=5 hour

The pore volume 1H of V1: pore diameter X ± 1.0nm: heating time=1 hour

The complete middle pore volume of V0: pore diameter 2.0-50nm

And, also can see diffraction maximum from graphite crystal.Therefore, these samples are such electrode materials, that is: has the pores that electrode material had such as being suitable for high static capacity and heavy-current discharge in a large number, promptly on the pore inner surface, form the pore in the abundant aperture of electric double layer equally, and the easy pore in movable abundant aperture in pore such as organic bath ion, inorganic electrolyte ion or these solvation electrolyte ions, and has electrode material by the resulting diffraction maximum from graphite crystal of X-ray diffraction.

Also have, with regard to the few carbonization sample 1 of Co addition, carbonization sample 6, activation sample 10, though in scope, have the maximum that fine pore distributes less than pore diameter 2.0nm, but pore diameter x ± α nm (3.0≤x＜10, α=1.0: 15% of the complete middle pore volume of the not enough pore diameter 2.0-50nm of the pore volume distribution of this pore diameter), in this scope, do not have the maximum of fine pore distribution, and do not see diffraction maximum from graphite crystal.

Also have, with regard to carbonization sample 5 with too much Co addition, carbonization sample 9, activation sample 13, though near 20-40nm, have the maximum that fine pore distributes, but pore diameter x ± α nm (3.0≤x＜10, α=1.0: 15% of the complete middle pore volume of the not enough pore diameter 2.0-50nm of the pore volume distribution of this pore diameter), in this scope, do not have the maximum of pore distribution, and do not see diffraction maximum from graphite crystal.

Therefore, these samples are such electrode materials, that is: do not have on the pore surface the same pore that forms the abundant aperture of electric double layer in a large number, do not have in a large number the organic bath ion, inorganic be the electrode material of the pore in the electrolyte ion etc. of electrolyte ion or these solvations abundant aperture of in pore, moving easily.

The fine pore distribution of char-forming material 1,2,3,5 is shown as an example on Fig. 1.Transverse axis is represented pore diameter, and the longitudinal axis is represented the pore volume in this pore diameter.Can find out by this figure, in the sample 2,3 in pore diameter x ± α nm (3.0≤x＜10, α=1.0: have the maximum that special fine pore distributes the distribution of this pore diameter) significantly.

Embodiment 2

To 100 weight portions with embodiment 1 identical granular phenol resin in add and to convert with Co that to become 5 weight portions such, and the cobalt chloride solution of adjusting through over-richness, after fully mixing by blender, following dry 24 hours in 110 ℃ in atmosphere, be warming up to fixed temperature by electric furnace programming rate with 50 ℃/hour in blanket of nitrogen then, then under this temperature after activating 1 hour nitrogen/steam (=1/1) mixed-gas atmosphere under, cool off, manufactured experimently 400 ℃ of activation samples (activation sample 14), 550 ℃ of activation samples (activation sample 15), 700 ℃ of activation samples (activation sample 16).In addition, the programming rate with 50 ℃/hour in blanket of nitrogen is warming up to given temperature, keeps cooling off after 5 hours, has manufactured experimently 550 ℃ of carbonization samples (carbonization sample 15), 1500 ℃ of carbonization samples (carbonization sample 18).Each sample fully cleans successively and removes with rare nitric acid, ion exchange water, distilled water after the remaining Co, and drying is 3 hours under 115 ℃.

Identically with embodiment the sample of making has as mentioned above been measured various rerum naturas be listed in table 2.As seen from Table 2, in the carbonization sample 3,18 of the activation sample 16 of 700 ℃ of activation and 1000 ℃, 1500 ℃ carbonizations, in pore diameter x ± α nm (3.0≤x＜10, α=1.0: the distribution of this pore diameter), have the maximum that special fine pore distributes, and a V ₁/ V ₀20-56% also is shown.And, also seen diffraction maximum from graphite crystal.

Therefore, these samples are such electrode materials, that is: has the pore of electrode materials such as being suitable for high direct capacitance and heavy-current discharge in a large number, promptly on the pore inner surface, form the sufficient aperture of electric double layer pore equally, and the organic system electrolyte ion, inorganic be the pore in the electrolyte ion etc. of electrolyte ion or these solvations abundant aperture of in pore, moving easily, but also have electrode material by the resulting diffraction maximum from graphite crystal of X-ray diffraction.

And, also can find out, activation temperature be 400 ℃, 550 ℃ activation sample 14,15 and carburizing temperature be 550 ℃ carbonization sample 17 in, heat treatment temperature is low, pore forms insufficient and in the mesopore zone, pore is undeveloped.In addition, also do not see diffraction maximum from graphite crystal.

Therefore, these samples are such electrode materials, that is: little measurer has the same pore that forms the abundant aperture of electric double layer on the pore inner surface, so also little measurer have the organic system electrolyte ion, inorganic be the electrode material of the pore in the electrolyte ion etc. of electrolyte ion or these solvations abundant aperture of in pore, moving easily.

Table 2

Sample	Raw material (weight portion)	Co addition (weight portion)	Heat-treat condition (temperature * time)	The pore diameter (nm) of the maximum that pore distributes	The pore volume of pore diameter X ± 1.0nm (V1)
						Activation sample 14	Phenolic resins 100	5	400 ℃ * 1H activation	0.7	0.001
Activation sample 15	Phenolic resins 100	5	550 ℃ * 1H activation	0.7	0.002
						Activation sample 16	Phenolic resins 100	5	700 ℃ * 1H activation	4.0	0.025
Carbonization sample 17	Phenolic resins 100	5	550 ℃ * 5H carbonization	0.7	0.002
						Carbonization sample 3	Phenolic resins 100	5	1000 ℃ * 5H carbonization	4.0	0.099
Carbonization sample 18	Carbon particulate 100	5	1500 ℃ * 5H carbonization	4.0	0.018

Sample	The complete middle pore volume (V0) of pore diameter 2.0-50nm	V1/V0 (％)	Specific area (m 2/g)	Elementary analysis value (%)			X ray is identified thing
								?C	?H	?N
				Activation sample 14	0.012	8.3					22	?72.09	?6.25	?0.82	?Co
Activation sample 15	0.016	12.5	86				?83.56	?4.93	?0.93	?Co
				Activation sample 16	0.099	25.3					699	?93.34	?1.85	?0.83	?Co、C
Carbonization sample 17	0.032	6.3	2				?82.34	?5.87	?0.97	?Co
				Carbonization sample 3	0.175	56.6					587	?97.18	?0.60	?0.92	?Co、C
Carbonization sample 18	0.089	20.2	39				?99.02	?0.38	?0.51	?Co、C

X: pore diameter 3≤X＜10 5H: heating time=5 hour

The pore volume 1H of V1: pore diameter X ± 1.0nm: heating time=1 hour

The complete middle pore volume of V0: pore diameter 2.0-50nm

Embodiment 3

In the phenolic resins identical of 100 weight portions, add with embodiment 1 by metal convert become 5 weight portion additions such, through the ferric chloride in aqueous solution that over-richness is adjusted, fully mix by mixer, in atmosphere in 110 ℃ dry 24 hours down.Dry sample is placed electric furnace and rises to 900 ℃ in blanket of nitrogen with 50 ℃/hour programming rate, after keeping 5 hours under this temperature, cool off, manufactured experimently carbonization sample 19.

Measured the X-ray diffraction analysis of fine pore distribution as the carbonization sample 19 of above-mentioned made, pore volume, CHN elementary analysis, Cu-K α line.It the results are shown in table 3.About the CHN elementary analysis, be the assay value of each sample of cleaning by rare nitric acid, and, then provide unwashed sample the parsing and the X-ray diffraction of fine pore.

Table 3

Sample	Carbonization sample 19
		Raw material (weight portion)	Phenolic resins 100
Metal addition metal species (weight portion)	Fe 5
		Heat-treat condition (℃)	900 ℃ * 5H of carbonization
Complete middle pore volume (V0) V1/V0 (%) of pore volume (V1) the pore diameter 2.0-50nm of pore diameter X (nm) pore diameter X ± 1.0nm of the maximum that fine pore distributes	3.0 0.041 0.132 31.3
		Specific area (m 2/g)	65
C elementary analysis value (%) H N	96.23 1.08 0.35
		X ray is identified thing	Fe，C

X: pore diameter 3≤X＜10 5H: heating time=5 hour

The pore volume of V1: pore diameter X ± 1.0nm

The complete middle pore volume of V0: pore diameter 2.0-50nm

As seen from Table 3, be in the carbonization sample 19 of the mixed chlorinated iron carbonization trial-production of raw material with the granular phenol resin, near pore diameter 3.0nm, have the maximum that gem-pure fine pore distributes.Can find out by this result, (3.0≤x＜10, α=1.0: the pore volume distribution of this pore diameter) has complete middle more than 15% of pore volume of pore diameter 2.0-50nm to obvious pore diameter x ± α nm in this sample, has the maximum that pore diameter distributes in this scope.And, also seen diffraction maximum from graphite crystal.

Therefore, this sample is such electrode material, that is: has a pore of electrode materials such as being suitable for high static capacity and heavy-current discharge, promptly has the same pore that forms the abundant aperture of electric double layer on the pore inner surface in a large number, especially have the organic system electrolyte ion, inorganic be the pore in the abundant aperture of in pore, moving easily such as electrolyte ion or these solvation electrolyte ions, and have electric material by the resulting diffraction maximum from graphite crystal of X-ray diffraction.

Comparative example 1

Granular phenol resin (Kanebo Ltd's system: Bellpear R800) place electric furnace with average grain diameter 20 μ m, and the programming rate with 30 ℃/hour is warming up to fixed temperature in blanket of nitrogen, 700 ℃ of carbonization samples (carbonization duplicate 20), 1000 ℃ of carbonization samples (carbonization duplicate 21) have been manufactured experimently in cooling after this temperature decline keeps 5 hours.In addition, by in nitrogen/steam (=1/1) mixed atmosphere,, 800 ℃ of activation samples (activation duplicate 22), 1000 ℃ of activation samples (activation duplicate 23) have been manufactured experimently with given temperature-activated 1 hour.Similarly to Example 1, carried out its characteristic measurement to comparing sample 20-23.It the results are shown in table 4.

As seen from Table 4, carbonization duplicate 20,21 is respectively 0.28cm in the pore volume value of its pore diameter 2.0-50nm ³/ g, 0.010cm ³/ g is little, forms mesopore hardly.Also have, and pore diameter x ± α nm (3.0≤x＜10, α=1.0: 15% of the complete middle pore volume of the not enough pore diameter 2.0-50nm of the pore volume distribution of this pore diameter), and in this scope, do not see the maximum that fine pore distributes.In addition, activation duplicate 22,23, specific area is big, the micropore prosperity also has the maximum that fine pore distributes near pore diameter 0.8nm, but pore diameter x ± α nm (3.0≤x＜10, α=1.0: 15% of the complete middle pore volume of the not enough pore diameter 2.0-50nm of the pore volume distribution of this pore diameter), and in this scope, do not see the maximum that fine pore distributes.That is to say, can find out that the pore volume that does not obtain pore diameter x ± 1.0nm (3.0≤x＜10) in not adding the duplicate 20-23 of transistion metal compound becomes the electrode material more than 15% of the complete middle pore volume of pore diameter 2.0-50nm.And, do not see diffraction maximum from graphite crystal yet.

Therefore, can find out: these samples do not have on the pore surface the same pore that forms the abundant aperture of electric double layer in a large number, especially do not have in a large number the organic system electrolyte ion, inorganic be the pore in the electrolyte ion etc. of electrolyte ion or its solvation abundant aperture of in pore, moving easily.

Table 4

Sample	Duplicate 20	Duplicate 21	Duplicate 22	Duplicate 23
					Raw material (weight portion)	Phenolic resins
100	100	100	100
				Transition metal addition (weight portion)		0	0	0	0
Heat-treat condition	700 ℃ * 5H carbonization	1000 ℃ * 5H carbonization	800 ℃ * 1H carbonization		1000 ℃ * 1H carbonization
				The pore diameter of the maximum (nm) that fine pore distributes		0.7	0.7	0.8	0.8
The pore volume of pore diameter X ± 1.0nm (V1)	0.004	0.000	0.006		0.014
				The complete middle pore volume (V0) of pore diameter 2.0-50nm		0.028	0.010	0.043	0.098
V1/V0 (％)	14.3	0.0	14.0		14.3
				Specific area (m 2/g)		15	27	965	1825
C elementary analysis value (%) H N	94.57 1.84 0.73	98.76 0.59 0.83	94.91 1.39 0.68		98.25 0.72 0.74
				X ray is identified thing		Do not have	Do not have	Do not have	Do not have

The pore volume 5H of V1: pore diameter X ± 1.0nm: heating time=5 hour

Pore volume 1H in V0: pore diameter 2.0-50nm complete: heating time=1 hour

Embodiment 4

The commercially available broken shape of each 100 weight portion or cylindric cocoanut shell carbon, coke, phenolic resins carbon are immersed in the copper chloride solution, and converting with Cu becomes 2 weight portions and has adjusted addition like that.After this, by in atmosphere, placing electric furnace in 110 ℃ of following samples of dry 24 hours, in blanket of nitrogen, be warming up to 900 ℃ and kept 2 hours, manufactured experimently cocoanut shell, coke, the carbonization sample 24 of phenolic resins carbon, the carbonization sample 25 of initial feed with 30 ℃/hour programming rate.After the part of sample was cleaned with rare nitric acid, residue Cu had been removed in fully washing again.Identical with embodiment 1, resulting sample is carried out physical property measurement.The various rerum naturas of the raw material rerum natura of carbonization sample 24,25, trial-production sample are all listed in down in the tabulation 5.

As seen from Table 5: even still can make such electrode material in the different sample 24,25 of initial feed, promptly (3.0≤x＜10, α=1.0: the pore volume distribution of this pore diameter) accounts for the electrode material more than 15% of the complete middle pore volume of pore diameter 2.0-50nm to its pore diameter x ± α nm.In addition, also see diffraction maximum from graphite crystal.

Table 5

Sample	Carbonization sample 24	Carbonization sample 25
			Material shape raw materials size specific area (m 2/ g) (weight portion)	The broken shape of coke (500-2000 μ m) 23 100	The cylindric 2mm Φ of phenolic resins carbon, 4-8mmL 12 100
Cu addition (weight portion)	2	2
			Heat-treat condition (temperature * hour)	900 ℃ * 2 hours	900 ℃ * 2 hours
The pore diameter of the maximum (nm) that fine pore distributes	3.6	4.2
			The pore volume of pore diameter X ± 1.0nm (V1)	0.029	0.090
The complete middle pore volume (V0) of pore diameter 2.0-50nm	0.104	0.132
			V1/V0 (％)	27.9	68.2
Specific area (m 2/g)	27	15
			C elementary analysis value (%) H N	95.36 1.27 1.32	96.72 0.97 0.83
X ray is identified thing	Cu，C	Cu，C

X: pore diameter 3≤X＜10

The pore volume of V1: pore diameter X ± 1.0nm

The complete middle pore volume of V0: pore diameter 2.0-50nm

Therefore, these samples are such electrode materials, that is: has the pore of electrode materials such as being suitable for high static capacity and heavy-current discharge in a large number, promptly on the pore inner surface, form the pore in the abundant aperture of electric double layer equally, especially in a large number have the organic system electrolyte ion, inorganic be the pore in the electrolyte ion etc. of electrolyte ion or its solvation abundant aperture of in pore, moving easily, and the electrode material that has that X-ray diffraction obtains from the diffraction maximum of graphite crystal.

Embodiment 5

By chelating resin (Mitsubishi Chemical's system: feed the nickel chloride aqueous solution of 1.0 mol CR-11), make Ni of in exchange column, filling ²⁺After ion exchanges, drying is 12 hours under 110 ℃, under blanket of nitrogen, be warmed up to fixed temperature and kept 3 hours from room temperature, manufactured experimently 400 ℃ of samples of carburizing temperature (carbonization sample 26), 550 ℃ of samples of carburizing temperature (carbonization sample 27), 700 ℃ of samples of carburizing temperature (carbonization sample 28), 800 ℃ of samples of carburizing temperature (carbonization sample 29), 900 ℃ of samples of carburizing temperature (carbonization sample 30) with 5 ℃/component velocity.In addition, by under blanket of nitrogen, begin to heat up from room temperature with 5 ℃/component velocity, at CO ₂To keeping 1 hour under the fixed temperature, 700 ℃ of samples of activation temperature (activation sample 31), 800 ℃ of samples of activation temperature (activation sample 32) have been manufactured experimently under/N (=1/1) the gaseous mixture atmosphere.

Various character such as the creating conditions of sample of trial-production, the evaluation thing of X-ray diffraction, specific area, fine pore distribution, pore volume are listed in table 6; The example that pore distributes is listed in Fig. 2-5; One example of X-ray diffraction image is listed in table 6.

Can find out from table 6, even adding metal is under the situation of Ni, be lower than in 600 ℃ of carbonization samples 26,27 in carburizing temperature, the maximum that fine pore distributes is in respectively this micropore one side respectively, and pore diameter x ± α nm (3.0≤x＜10, α=1.0: 15% of the complete middle pore volume of the not enough pore diameter 2.0-50nm of the pore volume distribution of this pore diameter), in the maximum of the not shown pore diameter of this scope.This can be speculated as: the pore that does not form the mesopore zone because carburizing temperature is low.In addition, also can find out, as carbonization sample 28,29,30, activation sample 31,32, in carburizing temperature more than 600 ℃ and activation temperature, the maximum that near the fine pore that forms diameter 4nm distributes.And, can find out that also (3.0≤x＜10, α=1.0: the pore volume distribution of this pore diameter) becomes big to pore diameter x ± α nm, has formed special fine pore and has distributed.Also seen diffraction maximum simultaneously from graphite crystal.

Therefore, these samples are such electrode materials, that is: has the pore of the electrode material that is suitable for high static capacity and heavy-current discharge in a large number, promptly on the thin surface of endoporus, form the pore in the abundant aperture of electric double layer equally, especially in a large number have the organic system electrolyte ion, inorganic be the pore in the abundant aperture of in pore, moving easily such as electrolyte ion or its solvation electrolyte ion, and have electrode material by the resulting diffraction maximum from graphite crystal of X-ray diffraction.

Table 6

Sample	Metal addition metal species (weight portion)	Heat-treat condition (temperature * time)	The pore diameter (nm) of the maximum that fine pore distributes	The pore volume of pore diameter X ± 1.0nm (V1)	The complete middle pore volume (V0) of pore diameter 2.0-50m	?V1/V0 ?(％)	Specific area (m 2/g)	The X line is identified thing
									Carbonization sample
26	Ni 28.0	400 ℃ * 3H carbonization	0.62	0.005	0.041	12.2	191	?Ni
									Carbonization sample
27	Ni 26.8	550 ℃ * 3H carbonization	0.78	0.014	0.104	13.5	236	?Ni
									Carbonization sample
28	Ni 28.4	700 ℃ * 3H carbonization	4.00	0.108	0.177	61.0	109	?Ni、C
									Carbonization sample 29	Ni 28.4	800 ℃ * 3H carbonization	4.03	0.121	0.166	73.3	97	?Ni、C
Carbonization sample
	30	Ni 30.2	900 ℃ * 3H carbonization	4.00	0.138	0.170	81.2	99	?Ni、C
Activation sample 31										Ni 37.0	700 ℃ * 1H activation	3.96	0.167	0.222	75.2	100	?Ni、C
	Activation sample 32	Ni 48.2	800 ℃ * 1H activation	3.93	0.186	0.265	70.2	109	?Ni、C

X: pore diameter 3≤X＜10 3H: heating time=3 hour

The pore volume 1H of V1: pore diameter X ± 1.0nm: heating time=1 hour

The complete middle pore volume of V0: pore diameter 2.0-50nm

Also have, X-ray diffraction identifies that the analysis result of thing can find out from Fig. 6, in the carbonization sample 28,30 that carries out carbonization treatment more than 600 ℃, except the nickel peak, has also observed the peak of graphite crystal near 2 θ=26.This expression: these samples are the graphited electrode materials of part.In general, for making the carbide graphitization, then need 1500 ℃-2000 ℃ high temperature.But the present invention shows: even carbonization also produces the part graphitization under the low temperature about 700 ℃.

Embodiment 6

Made easy double-layer capacitor as shown in Figure 8.Fig. 8 illustrates the cross section structure of the double-layer capacitor of having manufactured experimently.Will by carbonization sample 8,28 that embodiment 1-5 manufactured experimently, activation sample 12,16 and by 6 kinds of samples of the duplicate 21,22 of comparative example trial-production with rare nitric acid, ion exchange water and distilled water etc. fully after the cleaning, drying is 3 hours under 115 ℃, has made electrode material.

The aqueous sulfuric acid of each electrode material with the 30wt% that uses as electrolyte mixed, and dipping is made form slurry in a vacuum.

Plate-like platinum plate as collector body 2 used thickness 1mm, external diameter 18mm, make this collector body 2 with as thickness 0.5mm, the internal diameter 3mm of liner 4 usefulness, the plate-like silicon rubber crimping of external diameter 18mm, in by the hole of platinum plate and the formed degree of depth 0.5mm of silicon rubber, internal diameter 3mm, fill the pulp-like electrode material 1 of dipping sulfuric acid, it is made polarizing electrode.Concerning each electrode material 1, this polarizing electrode is respectively prepared 2, and between these 2, hold under the arm into the plate-like polypropylene division board of thickness 25 μ m, external diameter 18mm and make both mutually opposed.Secondly, will for the terminal board 5 that takes out the stainless steel that terminal uses from both sides and collector body 3 crimping.Especially, for fixing, carry out 10kg from the upside of the terminal board 5 of stainless steel and increase the weight of.

Obtain like this utilizing 6 kinds of the water system double-layer capacitors of 6 kinds of electrode materials of the present invention and respectively its static capacity and rate of change of capacitance being estimated, its result lists table 7.

As seen from table, carbonization sample of the present invention 8,28, activation sample 12,16 by embodiment 1-5 trial-production have in the electrolyte sulfate ion immersion pore in a large number, the same electric double layer that forms on the pore inner surface, and the pore in this ion easy abundant aperture of moving in pore, so be electrode material with high static capacity.

In addition, can find out also that carbonization sample of the present invention 8,28, activation sample the 12, the 16th by embodiment 1-5 trial-production also are suitable for the high electrode material of the little discharging current of volume change rate.This also can think: identical with the static capacity height, electrode material of the present invention has the pore in the abundant aperture that its sulfate ion flows easily in pore, and have by X-ray diffraction obtain from due to the diffraction maximum of graphite crystal.

On the other hand, the duplicate 21,22 of comparative example trial-production owing to do not have in large quantities that sulfate ion enters in the pore on the pore inner surface the same pore that forms the abundant aperture that electric double layer and this ion move easily in pore, so be the electrode material that impossible have high static capacity.

Table 7

Sample	Metal addition metal species (weight portion)	Heat-treat condition (temperature * time)	The pore diameter X (nm) of the maximum that fine pore distributes	(V1)	(V0)	V1/V0 (％)	Specific area (m 2/g)	Static capacity (F/g)	Volume change rate (%)
										Carbonization sample 8	Co 5.0	1000 ℃ * 5H carbonization	4.0	?0.098	?0.334	?29.3	?1415	?71	-19
Activation sample 12	Co 5.0	800 ℃ * 1H activation	4.0	?0.141	?0.368	?38.3	?1567	?73	-16
										Activation sample 16	Co 5.0	700 ℃ * 1H activation	4.0	?0.025	?0.099	?25.3	?699	?67	-16
Carbonization sample 28	Ni 28.4	700 ℃ * 3H carbonization	4.0	?0.108	?0.177	?61.0	?109	?62	-23
										Duplicate 21	Do not have 0.0	1000 ℃ * 5H carbonization	0.7	?0	?0.010	?0	?27	?21	-47
Compare test portion 22	Do not have 0.0	800 ℃ * 1H activation	0.8	?0.006	?0.043	?14.0	?965	?48	-53

X: pore diameter 3≤X＜10 1H: heating time=1 hour

The pore volume 3H of V1: pore diameter X ± 1.0nm: heating time=3 hour

Pore volume 5H in V0: pore diameter 2.0-50nm complete: heating time=5 hour

Can find out that also by the comparative example the 21, the 22nd of comparative example trial-production, rate of change of capacitance is unsuitable for the electrode material of heavy-current discharge greatly.This can think: identical with the not shown high value of static capacity is because do not have sulfate ion in pore easily due to the pore in mobile abundant aperture.

Embodiment 7

Identical with embodiment 6, will by carbonization sample 8,28 that embodiment 1-5 manufactured experimently, activated material 12,16 and by 6 kinds of samples of the duplicate 22,23 of comparative example trial-production with rare nitric acid, ion exchange water and distilled water etc. fully after the cleaning, drying is 3 hours under 115 ℃, has made electrode material.Made non-water system double-layer capacitor with this electrode material.10 parts of electric conducting materials electrification carbon blacks (Denka Black) (electrochemical industry Co., Ltd. system) of interpolation and 10 parts of jointing material fluororesin (the system teflon 6J of fluorine chemistry Co., Ltd. of Mitsui Du Pont) are also mixed in 80 parts of these electrode materials, then it are pressed into the disc type electrode of diameter 20mm.This electrode PVDF utmost point (Japanese milli pore Co., Ltd. system) is made division board, the propyl carbonate (1 mole/1 liter) of etamon tetrafluoride boron as electrolyte, is obtained non-water system double-layer capacitor, this formation is shown in Fig. 9.

Table 8

Sample	Metal addition metal species (weight portion)	Heat-treat condition (temperature * hour)	The pore diameter X (nm) of the maximum that fine pore distributes	(V1)	(V0)	V1/V0 (％)	Specific area (m 2/g)	Static capacity (F/g)
									Carbonization sample 8	Co 5.0	1000 ℃ * 5H carbonization	4.0	?0.098	?0.334	?29.3	?1415	?36
Activation sample 12	Co 5.0	1000 ℃ * 1H activation	4.0	?0.141	?0.368	?38.3	?1557	?39
									Activation sample 16	Co 5.0	700 ℃ * 1H activation	4.0	?0.025	?0.099	?25.3	?699	?33
Carbonization sample 28	Ni 28.4	700 ℃ * 3H carbonization	4.0	?0.108	?0.177	?61.0	?109	?32
									Duplicate 22	Do not have 0.0	800 ℃ * 1H activation	0.8	?0.006	?0.043	?14.0	?965	?22
Compare test portion 23	Do not have 0.0	1000 ℃ * 1H activation	0.8	?0.014	?0.098	?14.0	?1825	?26

X: pore diameter 3≤X＜10 1H: heating time=1 hour

The pore volume 3H of V1: pore diameter X ± 1.0nm: heating time=3 hour

Pore volume 5H in V0: pore diameter 2.0-50nm complete: heating time=5 hour

As seen from table, carbonization sample of the present invention 8,28, activation sample 12,16 by embodiment 1-5 trial-production have in the electrolyte etamon tetrafluoride boron ion immersion pore, the same electric double layer that forms on the pore inner surface, and the pore in this ion easy abundant aperture of moving in pore, so be electrode material with high static capacity.

On the other hand, also can find out, not having etamon tetrafluoride boron ion in a large number by the duplicate 22,23 of comparative example trial-production enters in the pore and form electric double layer equally on the pore inner surface, and the pore in this ion easy abundant aperture of moving in pore, so be the electrode material that impossible have high static capacity.

Embodiment 8

After adding the aqueous metal salt of 1.0 mol in sawdust that below the 1.0mm that is respectively 25g, sieves and the bamboo that is cut to 5mm * 5mm * 20mm and at room temperature flooding 24 hours from China fir, filter out sawdust, bamboo by aqueous metal salt, and at room temperature dry 3 days.In blanket of nitrogen in under the fixed temperature to sawdust, bamboo carbonization 1 hour after, cooled off, manufactured experimently 400 ℃ of carbonization samples of sawdust (carbonization sample 33), 550 ℃ of carbonization samples of sawdust (carbonization sample 34), 800 ℃ of carbonization samples of sawdust (carbonization sample 35), 550 ℃ of carbonization samples of bamboo (carbonization sample 36), 800 ℃ of carbonization samples of bamboo (carbonization sample 37).Have again, in sawdust, do not add iron nitrate aqueous solution but use iron chloride, nickel nitrate, cobalt nitrate aqueous solution at room temperature to flood respectively 24 hours, leach sawdust by each aqueous metal salt, and after at room temperature dry 3 days, in the nitrogen atmosphere 800 ℃ of following carbonizations after 1 hour, cool off, manufactured experimently iron chloride carbonization sample (carbonization sample 38), nickel nitrate carbonization sample (carbonization sample 39), cobalt nitrate carbonization sample (carbonization sample 40).

Table 9

Sample	Raw material	Transition metal	Heat-treat condition (temperature * time)	The complete middle pore volume (V0) of pore diameter 2.0-50nm	V1/V0 (％)	Specific area (m 2/g)	X ray is identified thing
								Carbonization sample 33	Sawdust	Fe	400 ℃ * 1H carbonization	0.017	14	9	Do not have
Carbonization sample 34	Sawdust	Fe	550 ℃ * 1H carbonization	0.047	13	410	Fe
								Carbonization sample 35	Sawdust	Fe	800 ℃ * 1H carbonization	0.210	21	160	Fe、C
Carbonization sample 36	Bamboo	Fe	550 ℃ * 1H carbonization	0.019	14	480	Do not have
								Carbonization sample 37	Bamboo	Fe	800 ℃ * 1H carbonization	0.185	17	190	Fe、C
Carbonization sample 38	Sawdust	Fe	800 ℃ * 1H carbonization	0.135	21	390	Fe、C
								Carbonization sample 39	Sawdust	Ni	800 ℃ * 1H carbonization	0.074	26	300	Ni、C
Carbonization sample
	40	Sawdust	Co	800 ℃ * 1H carbonization	0.177	24	130	Co、C

The pore volume of V1: pore diameter X ± 1.0nm

The complete middle pore volume of V0: pore diameter 2.0-50nm

1H: heating time=1 hour

X-ray diffraction for the fine pore distribution of the sample of above-mentioned made, pore volume, Cu-K α line is measured, and its measurement result is listed in table 9.As seen from Table 9: the carbonization sample 35 of 800 ℃ of carbonizations of sawdust, and in the carbonization sample 37 of 800 ℃ of carbonizations, iron chloride carbonization sample (carbonization sample 38), nickel nitrate carbonization sample (carbonization sample 39), cobalt nitrate carbonization sample (carbonization sample 40), the pore volume of its pore diameter 2.0-50nm is respectively 0.210cm ³/ g, 0.185cm ³/ g, 0.135cm ³/ g, 0.074cm ³/ g, 0.177cm ³/ g sees that very big middle pore volume is arranged; This pore volume accounts for complete middle more than 15% of pore volume of pore diameter 2.0-50nm, also sees the diffraction maximum from graphite crystal.

Therefore, these samples are such electrode materials, that is: has the pore of the electrode material that is suitable for high static capacity and heavy-current discharge in a large number, promptly on the pore inner surface, form the pore in the abundant aperture of electric double layer equally, especially in a large number have the organic system electrolyte ion, inorganic be the pore in the electrolyte ion etc. of electrolyte ion or its solvation abundant aperture of in pore, moving easily, but also have electrode material by the resulting diffraction maximum from graphite crystal of X-ray diffraction.

Can find out that also in the carbonization sample 33,34,36 that carburizing temperature is 400 ℃, 550 ℃, heat treatment temperature is low, pore forms insufficient and is undeveloped at mesopore zone pore.And, do not see diffraction maximum from graphite crystal yet.

Therefore, these samples are such electrode materials, that is: do not have on the pore inner surface the same pore that forms the abundant aperture of electric double layer in a large number, especially do not have in a large number the organic system electrolyte ion, inorganic be the electrolyte ion etc. of electrolyte ion or its solvation electrode material of the pore in mobile abundant aperture easily in pore.

Comparative example 2

Sawdust that sieves below the 1.0mm from China fir with 25g and the bamboo that cuts into 5mm * 5mm * 20mm in to carrying out carbonization in 1 hour and cooling under the fixed temperature, have been manufactured experimently 400 ℃ of carbonization samples of sawdust (carbonization duplicate 24), 550 ℃ of carbonization samples of sawdust (carbonization duplicate 25), 800 ℃ of carbonization samples of sawdust (carbonization duplicate 26), 800 ℃ of carbonization samples of bamboo (carbonization duplicate 27) in blanket of nitrogen respectively.Identical with embodiment 8,24-27 has carried out physical property measurement to these duplicates, and its measurement result is listed in table 10.

As seen from Table 10, carbonization duplicate 24,25,26,27, the pore volume value of its pore diameter 2.0-50nm is respectively 0.010cm ³/ g, 0.025cm ³/ g, 0.22cm ³/ g, 0.014cm ³/ g is smaller, forms mesopore hardly, and does not see the diffraction maximum from graphite crystal.

Therefore, also can find out, these samples do not have on the pore inner surface the same pore that forms the abundant aperture of electric double layer in a large number, especially do not have in a large number the organic system electrolyte ion, inorganic be the electrolyte ion etc. of electrolyte ion or its solvation pore in mobile abundant aperture easily in pore.

Table 10

Sample	Duplicate 24	Duplicate 25	Duplicate 26	Duplicate 27
					Raw material (weight portion)	Sawdust			Bamboo
100	100	100	100
				Transition metal adds (weight portion)		0	0	0	0
Heat-treat condition	400 ℃ * 1H carbonization	600 ℃ * 1H carbonization	800 ℃ * 1H carbonization		800 ℃ * 1H carbonization
				The complete middle pore volume (V0) of pore diameter 2.0-50nm		0.010	0.025	0.022	0.014
Specific area	9	470	470		10
				The X line is identified thing		Do not have	Do not have	Do not have	Do not have

1H: heating time=1 hour

Embodiment 9

The ion exchange resin of in splitter, filling (Mitsubishi Chemical society system: the copper nitrate aqueous solution that feeds 0.5 mol of three times of ion exchange capacities ion exchange resin C-467), after copper ion carried out ion-exchange, with its washing and air dry, after under 115 ℃ dry 12 hours, under blanket of nitrogen, be warming up to 800 ℃ and kept 3 hours from room temperature, manufactured experimently carbonization sample 41 with 5 ℃ of/minute intensification speed.Clean the part of carbonization sample 41 then with the 5M hydrochloric acid solution, after this copper in the stripping carbide boil in ion exchange water to remove hydrochloric acid and copper ion from carbide, manufactured experimently carbonization sample 42.

In addition, profit uses the same method after copper sulfate solution with 0.5 mol carries out ion-exchange to copper ion, and washing, air dry and at 110 ℃ down after dry 12 hours are warming up to 800 ℃ with 5 ℃/component velocity by room temperature under blanket of nitrogen, keep after 3 hours, at CO ₂Through activation back cooling in 0.5 hour, manufactured experimently activation sample 43 under/N (=1/1) the gaseous mixture atmosphere.And then,, in ion exchange water, boil after the copper in the stripping activator in a part of cleaning activation sample 43 with the 5M hydrochloric acid solution, from activator, remove hydrochloric acid and copper ion, manufactured experimently activation sample 44.And then, clean in the part of activation sample 44 and the stripping activator after the copper with the 5M hydrochloric acid solution again, in ion exchange water, boil, from activator, remove hydrochloric acid and copper ion, manufactured experimently the activation sample 45 of cleaning and strengthening.

Carbonization sample 41, carbonization sample 42, activation sample 43, activation sample 44, activation sample 45 are used as electrode respectively, identical with embodiment 6, obtain 5 kinds of water system double-layer capacitors, and measured static capacity separately.Especially, by 20 charging and dischargings repeatedly, the cycle characteristics of separately capacitor is estimated.

Various character such as the sample of being manufactured experimently is created conditions, specific area, fine pore distribution, pore volume and static capacity are listed in table 11, and the measurement result of the static capacity of measuring repeatedly for 20 times is listed in table 12.

Table 11

Sample	Raw material	Kinds of transition metals	Heat-treat condition (temperature * time)	Hydrochloric acid cleans
					Carbonization sample 41	Ion exchange resin C467	Cu	800 ℃ * 3H carbonization	×
Carbonization sample 42	Ion exchange resin C467	Cu	800 ℃ * 3H carbonization	○
					Activation sample 43	Ion exchange resin C467	Cu	800 ℃ * 3H carbonization, 750 ℃ * 0.5H activation	×
Activation sample 44	Ion exchange resin C467	Cu	800 ℃ * 3H carbonization, 750 ℃ * 0.5H activation	○
					Activation sample 45	Ion exchange resin C467	Cu	800 ℃ * 3H carbonization, 750 ℃ * 0.5H activation	◎

Sample	Cupric concentration (%)	V1	V0	V1/V0 (％)	Specific area (m 2/g)	Static capacity (F/g)
							Carbonization sample 41	34	0.031	0.071	43.7	454	105
Carbonization sample 42	1.4	0.101	0.209	48.3	956	140
							Activation sample 43	26	0.043	0.110	39.1	233	85
Activation sample 44	1.9	0.085	0.180	47.2	895	152
							Activation sample 45	0.002	0.039	0.146	26.7	900	76

X: pore diameter 3≤X＜10 1H: heating time=1 hour

The pore volume 3H of V1: pore diameter X ± 1.0nm: heating time=3 hour

The complete middle pore volume static capacity of V0: pore diameter 2.0-50nm: calculate according to the 1st charging cycle

Hydrochloric acid cleans: zero expression cleans, * expression is cleaned, ◎ represents to strengthen and cleans

As seen from Table 11, carbonization sample 41, carbonization sample 42, activation sample 43, activation sample 44, activation sample 45, (3.0≤x＜10, α=1.0: the pore volume distribution of this pore diameter) accounts for complete middle more than 15% of pore volume of pore diameter 2.0-50nm to its pore diameter x ± α nm.

Table 12

Sample	Carbonization sample 41	Carbonization sample 42	Activation sample 43	Activation sample 44	Activation sample 45
						Circulation	(F/g)	(F/g)	(F/g)	(F/g)	(F/g)
1	105	140	85	152	76
						2	109	143	84	152	76
3	110	142	83	152	75
						4	107	141	83	153	76
5	106	141	84	155	76
						6	104	142	82	155	76
7	105	141	81	157	76
						8	109	141	80	158	75
9	110	140	80	158	75
						10	111	140	80	158	75
11	107	142	78	158	75
						12	106	141	79	157	76
13	106	142	78	158	76
						14	107	141	79	157	76
15	108	141	80	158	75
						16	107	140	80	156	78
17	107	140	81	158	78
						18	108	142	80	157	76
19	106	141	80	157	76
						20	105	142	81	157	76

Table can be found out by 11, activation sample 41, carbonization sample 42, activation sample 43, activation sample 44 are such electrodes, that is: having the electrolyte sulfate ion in a large number immerses in the pore, the same electric double layer that forms on the pore inner surface, and the pore in this ion easy abundant aperture of moving in pore, the copper that contains simultaneously also helps to adsorb energy, is the electrode material with high static capacity therefore.And, also can find out, in carbon structure, firmly fixing copper, even therefore carry out charging and discharging repeatedly, also have stable static capacity.

Embodiment 10

To the granular phenol resin of the average grain diameter 20 μ m of 100 weight portions (Kanebo Ltd's system: Bellpear R 800) add to convert and become the such copper chloride solution of adjusting through over-richness of 10 weight portions by Cu, fully mix by mixer, following dry 2 hours in 110 ℃ in atmosphere, the sample of such drying is warming up to 800 ℃ and kept 3 hours with 5 ℃/minute speed from room temperature under blanket of nitrogen, has manufactured experimently carbonization sample 46.Then, clean the part of carbonization sample 46 and the copper in the stripping carbide with the 5M hydrochloric acid solution again, in ion exchange water, boil, and, manufactured experimently carbonization sample 47 by removing hydrochloric acid and copper ion in the carbide.

Have again, same phenolic resins (Kanebo Ltd's system: add Bellpear R800) to 100 weight portions by the such copper chloride solution of Cu conversion becoming 10 weight portions through the over-richness adjustment, fully mix by mixer, following dry 24 hours in 110 ℃ in atmosphere, the sample of such drying is warming up to 800 ℃ and kept 3 hours with 5 ℃/minute speed from room temperature under blanket of nitrogen, at CO ₂Activation sample 48 has been manufactured experimently in cooling after activation in 5 hours under/N (=1/1) the gaseous mixture atmosphere.One one that will activate sample 48 is then boiled in ion exchange water with after the copper in cleaning of 5M hydrochloric acid solution and the stripping activator, removes hydrochloric acid and copper ion from activator, has manufactured experimently activation sample 49.

Carbonization sample 46, carbonization sample 47, activation sample 48, activation sample 49 are used as electrode material respectively, similarly to Example 9, obtain 4 kinds of the double-layer capacitors of water system, respectively its static capacity is measured, and 20 times the circulation of each capacitor of charging and discharging is repeatedly estimated.

The various character and the static capacity of the sample condition of being manufactured experimently, specific area, fine pore distribution, pore volume etc. are listed in table 13; And the measurement result of the static capacity measured repeatedly for 20 times is listed in table 14.As seen from Table 13, carbonization sample 46, carbonization sample 47, activation sample 48, activation sample 49, (3.0≤x＜10, α=1.0: the pore volume distribution of this pore diameter) accounts for complete middle more than 15% of pore volume of pore diameter 2.0-50nm to its pore diameter x ± α nm.

Therefore, can find out, carbonization sample 46, carbonization sample 47, carbonization sample 48, carbonization sample 49 are such electrode materials, that is: having the electrolyte sulfate ion in a large number immerses in the pore and the same electric double layer that forms on the pore inner surface, and the pore in this ion easy abundant aperture of moving in pore, contained copper helps to adsorb energy simultaneously, is the electrode material with high static capacity therefore.In addition, copper is being firmly fixed in carbon structure, even the charging and discharging therefore by repeatedly still has stable static capacity.

Table 13

Sample	Raw material	Kinds of transition metals	Heat-treat condition (temperature * time)	Hydrochloric acid cleans
					Carbonization sample 46	Phenolic resins	Cu	800 ℃ * 3H carbonization	×
Carbonization sample 47	Phenolic resins	Cu	800 ℃ * 3H carbonization	○
					Carbonization sample 48	Phenolic resins	Cu	800 ℃ * 3H carbonization, 800 ℃ * 1H activation	×
Carbonization sample 49	Phenolic resins	Cu	800 ℃ * 3H carbonization, 800 ℃ * 1H activation	○
					Duplicate 21	Phenolic resins	-	1000 ℃ * 5H carbonization	×
Duplicate 22	Phenolic resins	-	800 ℃ * 1H carbonization	×

Test portion	Cupric concentration (%)	V1	V0	V1/V0 (％)	Specific area (m 2/g)	Static capacity (F/g)
							Carbonization sample 46	12.3	0.015	0.087	17	560	86
Carbonization sample 47	1.5	0.022	0.099	22	756	99
							Carbonization sample 48	11.3	0.029	0.132	22	780	87
Carbonization sample 49	2.2	0.048	0.176	27	880	101
							Duplicate 21	0	0	0.010	0	27	21
Duplicate 22	0	0.006	0.043	14	965	48

X: pore diameter 3≤X＜10 1H: heating time=1 hour

The pore volume 3H of V1: pore diameter X ± 1.0nm: heating time=3 hour

The complete middle pore volume static capacity of V0: pore diameter 2.0-50nm: calculate according to the 1st charging cycle

Hydrochloric acid cleans: zero expression cleaning, * cleaning of expression

Table 14

Sample	Carbonization sample 46	Carbonization sample 47	Activation sample 48	Activation sample 49
					Circulation	(F/g)	(F/g)	(F/g)	(F/g)
1	86	99	87	101
					2	84	98	86	102
3	82	99	85	100
					4	80	100	85	100
5	79	99	86	99
					6	79	98	85	99
7	80	99	87	101
					8	80	98	88	101
9	79	98	89	100
					10	78	97	90	98
11	78	98	89	99
					12	79	99	88	99
13	79	98	87	99
					14	79	99	86	98
15	78	98	85	99
					16	78	99	85	100
17	77	98	85	101
					18	79	98	84	101
19	79	98	84	100
					20	78	98	84	99

Claims (12)

1. electrode material, have active carbon and on active carbon, support transition metal or transistion metal compound, it is characterized in that, pore diameter x ± α nm, wherein, 3.0≤x＜10, α=1.0, pore volume account for more than 15% of pore volume in pore diameter 2.0-50nm complete, and contain transition metal or the transistion metal compound that 1-50wt% is selected from copper, iron, cobalt, nickel in the electrode material.

2. electrode material according to claim 1 is characterized in that, at pore diameter x ± α nm, wherein, 3.0≤x＜10, α=1.0 in the scope, have the maximum that fine pore distributes.

3. electrode material according to claim 1 and 2 is characterized in that, has the diffraction maximum from graphite crystal that is obtained by the x x ray diffraction.

4. electrode material according to claim 1 is characterized in that, transition metal or transistion metal compound are the compound of copper or copper.

5. described manufacturing method of electrode material of claim 1, it is characterized in that, in material with carbon element and/or material with carbon element predecessor, add at least after a kind of transition metal or transistion metal compound that is selected from copper, iron, cobalt, nickel, under 700-2000 ℃ of temperature, under nonoxidizing atmosphere, carry out carbonization, or under weak oxide atmosphere, activate.

6. manufacturing method of electrode material according to claim 5, it is characterized in that, described carbon material is cocoanut shell carbon, coke, charcoal, resin carbonation thing, bamboo carbide and composition thereof, and perhaps the predecessor of carbon material is cocoanut shell, coal, timber, resin, bamboo and composition thereof.

7. manufacturing method of electrode material according to claim 6 is characterized in that, the resin carbonation thing is the ion exchange resin carbide, and perhaps resin is an ion exchange resin.

8. manufacturing method of electrode material according to claim 6 is characterized in that, the resin carbonation thing is the phenolic resins carbide, and perhaps resin is a phenolic resins.

9. according to each described manufacturing method of electrode material of claim 5-8, it is characterized in that, in the material with carbon element of 100 weight portions or material with carbon element predecessor, add the transition metal or the transistion metal compound of 1-100 weight portion.

10. according to each described manufacturing method of electrode material of claim 5-8, it is characterized in that transition metal or transistion metal compound are metal dust or nitrate, acetate, sulfate, carbonate, phosphate, bromide, chloride, phosphide, oxide and hydroxide.

11. battery, it is characterized in that, use has active carbon and support the electrode material of transition metal or transistion metal compound on active carbon, this electrode material is pore diameter x ± α nm, wherein, 3.0≤x＜10, α=1.0, pore volume account for more than 15% of pore volume in pore diameter 2.0-50nm complete, and contain transition metal or the transistion metal compound that 1-50wt% is selected from copper, iron, cobalt, nickel in the electrode material.

12. double-layer capacitor, it is characterized in that, use has active carbon and support the electrode material of transition metal or transistion metal compound on active carbon, this electrode material is pore diameter x ± α nm, wherein, 3.0≤x＜10, α=1.0, pore volume account for more than 15% of pore volume in pore diameter 2.0-50nm complete, and contain transition metal or the transistion metal compound that 1-50wt% is selected from copper, iron, cobalt, nickel in the electrode material.

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